JPH11500972A - Coextrusion of liquid crystal and thermoplastic polymers for container molding - Google Patents

Abstract

(57) Abstract: A flat, substantially mechanically isotropic polymer film or sheet (38) that can be formed by laminating two or more films, preferably by coextrusion of a liquid crystal polymer film and a thermoplastic polymer film. ), Or tube. The liquid crystal polymer layer can be combined with one or more thermoplastic polymer layers in various configurations. Liquid crystals and thermoplastics can probably have controlled molecular orientation as well. The film (38) can be formed by passing the polymer through a set (32, 36) of coaxial and opposing two or three tubular rotors that define inner and outer annular polymer flow channels.

Description

DETAILED DESCRIPTION OF THE INVENTION         Coextrusion of liquid crystal and thermoplastic polymers for container molding Cross-reference of related applications   This application was filed on June 16, 1989, and filed with application number 07 / 367,433. It is based on PCT / US90 / 03394, filed June 18, 1990, which is a continuation-in-part application. No. 07 / 778,812 filed on December 12, 1991, issued on February 22, 1994 U.S. Patent No. 5,288,529, filed on March 24, 1994 General Assigned Application No. 08 / 217,236, filed September 23, 1993, pending No. 08 / 125,919, filed on September 23, 1993 and withdrawn It is a continuation-in-part application of application No. 08 / 126,043. Background of the Invention Field of the invention   The present invention relates to an aligned liquid crystal polymer (LPC) layer and a thermoplastic polymer (TP). ) And / or a method for molding a container comprising an LCP-TP blend layer. I do. More specifically, the present invention inherently retains its form and has previously been obtained. Extrusion blow molded with a more uniform coefficient of thermal expansion than those without substantial defects Molding of a laminated polymer container.   The present invention also provides at least one LCP layer and at least one TP layer. Having coextruded polymer structure and / or LCP-TP blend layer , At least the LCP layer has a controlled molecular orientation. Description of related technology   The invention generally relates to processing under conditions where the film has a controlled molecular orientation. , High molecular weight liquid crystal thermotropic or lyotropic polymer (homopolymer , From copolymers, etc.). these Polymers are generally of two classes: those modified in solution form, namely lyot Liquid crystal polymer and those modified by temperature changes, It is classified into a liquid crystal polymer. Expressions covering both types of polymers For the sake of simplicity, the disclosure herein will use the term “liquid crystal polymer” or LCP Is used.   In certain embodiments disclosed herein, the liquid crystal polymer is a thermoplastic polymer. -Extrude simultaneously.   The liquid crystal polymer in the present specification is composed of monomer repeating units constituting a polymer chain. Due to its nature, it is believed to have a fixed molecular form, such as linear. Linear Aligned polymers are also known as "rod-shaped" polymers. These liquid crystal polymers Is a typical, typical "coil" in which the molecular chains do not have a relatively fixed shape. "Thermoplastic" polymer. Some of these blends are liquid It has similar processing and functional properties as crystalline polymers, and to some extent these blurs. Is considered to be included in the invention disclosed herein.   A preferred LCP is Vectra^R(Made by Hoechst-Celanese), Xydar^R(Amoco Perfo rmance Products), Zenite^R HX type LCP (DuPont), Ekonol^RAnd S umikasuper^R(Sumitomo Chemical Industries, Ltd.), Rodrun^R(Made by Unitika Ltd.) and And Granlar^RAromatic copolyers exemplified by commercially available products such as (Granmont) It is of the steal class. Preferred "coiled" or thermoplastic polymers are , Polyethylene, polypropylene, ethylene vinyl alcohol, polyvinylidene Fluoride, polyetheretherketone, polyarylate, polyamide, poly Lamide-imide, polycarbonate, polyethylene terephthalate, polyethylene Lennaphthalate, polybutylene terephthalate, polybutylene naphthalate, Polyetherimide, polyimide, polyphenylene sulfide, polystyrene, Thermoplastics such as polyurethane, polyvinyl chloride and polyvinylidene chloride It is. These are typical examples and do not limit the present invention.   While liquid crystal polymer films have desirable qualities in many applications, It has significant disadvantages with regard to mechanical anisotropy. It is a high-gas barrier film and It is particularly useful for forming circuit boards. The gas barrier properties of LCP are typical Is 100 to 300 times better than polyethylene terephthalate, This makes it useful for food and beverage packaging applications. Bot Food packages, such as bottles, caps, trays, jars and other containers Benefits from the combination of high-oxygen and high-water vapor barriers inherent in P-films I can. Drinks such as bottles, bag-in-boxes and cap seals The charge package is also a high barrier LCP film layer incorporated in such a package. Can benefit as well. Accordingly, one object of the present invention is to provide an economical package. Food aging, taste and other desirable food and beverage characteristics. The use of an LCP barrier layer to improve the properties. Another purpose is Shelf life of beverages such as beer, wine, fruit juices and soft drinks While improving taste, carbon dioxide retention and other desirable properties.   However, previously, the mechanical properties of the liquid crystal polymer film or layer It was insufficient for their application. The LCP is pressed, as is possible with coil polymers. It cannot be blown and stretched after taking out. Because it is highly advanced in the die This is because the orientation is excessive. It is too weak in the non-oriented direction and in the semi-flow form In addition, it cannot be stretched after extrusion.   To improve its strength, the liquid crystal polymer film typically has a pair of coaxial Extrusion between concentric counter-rotating cylindrical dies To form a tube. This process is different for the inner and outer surfaces of the tube. Different orientations, which can add biaxial strength to the tube if desired. To allow blowing and stretching.   2A-2C are schematic diagrams of an extruded film showing a form of an oriented polymer material layer. You. In FIG. 2A, if there was no lateral or circumferential shear, the film would All molecules are in the machine direction, i.e., in the longitudinal direction relative to the direction of flow through the die. It has an oriented uniaxial orientation. In FIG. 2B, the film has a biaxial orientation. The molecules at the top of the film are oriented at an angle of + θ to the machining direction, On the other hand, the lower part of the film in FIG. 2B is at an angle of -θ with respect to the machining direction. Oriented. FIG. 2C shows that the polymer rods are randomly present on the film surface, Plane isotropic field that is not strongly oriented at any particular angle to the machining direction. Show Lum.   Biaxially oriented tubes are slit and spread apart to form a flat film structure be able to. However, the inventors of application Ser. I found a problem with this process that had not been done. Fill thus formed They do not want to stay flat. Pressing such film under heating But the film continues to cool after compression To obtain a tendency to curl. Briefly, film The two surface layers have different coefficients of thermal expansion (axial and lateral) with respect to the orientation of their molecules. (CTE). Generally, the lateral CTE is larger. Therefore As the sheet cools, each layer tries to shrink more in its own transverse direction I do. However, since the two layers are both part of the sheet, the sheet As a result, it cannot contract freely in any direction. As a result, stress Accumulates and makes the sheet bistable, thereby holding it in a plane Keep curl around one of two different axes without aggressive effort And easily take one of these two states.   As best understood, liquid crystal polymer films have this curl shape problem You. Because it is a fibril, that is, a relatively straight molecule Because it includes. The molecules are strongly oriented in the die and the flowing polymer is run It is much more anisotropic than regular coil polymers that tend to dam. coil The polymer tube or sheet blows and extends after it exits the die Thereby, the thickness can be biaxially reinforced throughout. Also when In each case, a reversing die is used to make the conventional polymer more isotropic. But shear Is the combination of shear and stretch much more critical to optimize in liquid crystal polymer extrudates? Is difficult. Because it is easily highly anisotropically oriented in the die is there. Stretching a polymer substantially transverse to its fibril orientation is Would not be possible.   Establish biaxial or multiaxial (particularly torsional nematic) orientation of molecules during flow If you use a reversing annular die to blow the extruded tube, Stretching is possible and effective.   However, as mentioned above, such a process is not dependent on the machining direction in which the extrusion occurs. Two layers in a film with complementary orientation on either side, eg +/− 45 ° To form As mentioned above, this was made from such an extruded tube. This leads to the disadvantage of curl formation in the liquid crystal polymer film sheet. Liquid crystal poly Mer films have low anisotropy due to transverse shear, which is It still curls later. This is because of the non-uniform CTE phenomenon described above. You. The film is orthotropic, that is, in a balanced biaxial film Curl is very important if it has the same characteristics in the orthogonal direction in the film plane Becomes   Often associated with films made by the tubular bubble process One problem is seaming. When joining, the film tube is pinch low Some known to flatten or "block" it as you move through it It is formed by the method described above.   These problems are due, at least in part, to the inherent properties of the tube extrusion process. System control and downstream processing, some starting with coagulation or cooling. In connection with the method of processing, perhaps also in part, upstream of poor doping uniformity.   The present inventors have found that the aforementioned problems with the film include extruded blow molded containers. It has been found that this also affects the extruded LCP molded product. For the latter, blow molding The process involves thin areas and splices in the LCP layer when applied to a conventional extruded parison. Includes transverse stretching that causes litting. Therefore, a further object of the invention is Will degrade the performance of LCP as a substantial splitting or barrier layer A multi-layer blow molded bottle having a uniform LCP layer that can be formed without other defects or It is to provide another container.   It is a further object of the present invention to provide one or more thermoplastic coiled polymer layers and / or Or co-extruding an oriented LCP layer having one or more LCP-thermoplastic blend layers Multi-layer LCP-thermoplastic or LCP-thermoplastic that can be molded into bottles, containers or vessels To produce a plastic blend structure.   There are no previously known techniques in the art that can solve these problems.   Published September 28, 1993, Hoechst-Celanese Corp. Jester and others transferred to the company U.S. Pat. No. 5,248,530 discloses a low melting point LCP layer and a high melting point Extrusion is disclosed. Jester et al. Have a high melting point LCP layer between two low melting point LCP layers. It is also disclosed that a sandwich is prepared.   US Patent Application No. 206,137, filed June 13, 1988; filed June 7, 1988 No. 203,329 filed; and No. 098,710 filed on Sep. 21, 1987 Nos. (All generally listed here) are all horizontal dimensions that affect the molecular orientation of the final product. To control the shear rate in the direction, the material flow rate, the blow molding speed and the draw ratio. Thus, a biaxially oriented, substantially two-layer liquid crystal polymer film is formed in an inverted annular die. Disclosed is a process for shaping to obtain two surface layers having a substantially +/- 45 degree orientation. (See also U.S. Patent Application No. 209,271 filed June 20, 1988) .   Nagasawa et al., JP-A-53-47460, include applying lateral shear to a dope. (FIGS. 2 and 3). See pages 8-9).   Other important prior art include:   Urasaki, JP-A-53-86798   Sugimoto et al., JP-A-54-44307   Fujii et al., JP-A-63-199622   Fujii et al., JP-A-63-173620   Inada et al., JP-A-52-109578   Miyamoto et al., JP-A-63-296920   Donald, U.S. Patent No. 3,279,501   Donald, U.S. Patent No. 3,404,203   Sharps, Jr. U.S. Pat.No. 4,496,413   Isayev et al., U.S. Pat.No. 4,728,698   Helminiak et al., US Patent No. 4,377,546 are included.   Corresponding disclosure of all prior art materials and patent applications mentioned herein Are expressly cited and regarded as part of the present specification. Summary of the Invention   The above problems in the prior art are due to the process and apparatus disclosed herein. Is substantially solved.   According to one embodiment of the present invention, a two-ring or three-ring tubular extrusion die is used. And co-extrude the liquid crystal polymer and thermoplastic polymer layers, e.g. Films or tubes can be formed. Dies with more rings The use of is also contemplated.   Another aspect of the invention is a co-extruded liquid crystal having substantially uniform mechanical properties and Any localization of the directional thermal expansion coefficient of the thermoplastic polymer film, especially its individual layers Despite local non-uniformity, it remains flat and has almost uniform heat in all directions. This is a method of forming a film having an expansion coefficient.   Another aspect is a relatively thin, perhaps relatively thick or thin inner portion -Extruded liquid crystal and thermoplastic polymer fill containing two outer surfaces capable of This is a method of forming a system. The inner portion has at least one controllable direction and And possibly also a second controllable direction. The The outer portion can be oriented in other controllable directions.   Preferably, at least the LCP layer has a controllable orientation. TP layer or layer The groups can be similarly oriented.   One LCP layer can be combined with, for example, two TP layers in any order. Wear. One of the two thermoplastic layers is between the LCP and the other thermoplastic. As an adhesive or “tie layer”. More generally, one or more LPCs Any combination of layers and one or more TP layers is also contemplated as part of the present invention.   According to one particular aspect of the invention, a relatively thick or thin inner portion is controlled. Have an orientation that is complementary to that of the two surface portions, and each of these portions The direction is preferably complemented by perhaps +/- 45 ° with respect to the machining direction in which the extrusion takes place. Specify the foot angle.   A method for producing this type of multiaxially oriented film from a liquid crystal polymer is as follows. (A) subjecting the axially flowable polymer material to lateral movement, thereby causing axial flow; (B) fix the micro-scale structural orientation thus obtained Process. The die for extruding this type of polymer film is described herein. Put on.   Yet another aspect is an LCP layer within the relatively thin or thick inner portion. And / or including a central core layer. Film structure in its central core layer Can be at or near the machining direction.   Also, the film structure generally has two outer sides oriented in a first controllable direction. Surface layers; each facing inside an outer surface layer that is generally oriented in a second controllable direction Two intermediate layers; and generally at or near the machining direction A central core layer sandwiched between the intermediate layers oriented in a third controllable direction May be included. The intermediate layer has an orientation that is complementary to that of other adjacent layers. You may have. Thus, each direction of orientation of each outer surface layer and adjacent intermediate layer is , May be defined equal and opposite angles to the machining direction in which the extrusion is performed. is there Alternatively, the orientation direction of each intermediate layer is between that of the adjacent outer layer and that of the central core layer. Thus gradually changing direction from the outer layer to the central core layer . Each orientation direction of the outer surface layer and the intermediate layer is preferably machined by extrusion. Defines equal and opposite angles to the direction.   In addition to the film structure described above, a further aspect of the invention is a multi-layer LCP-thermoplastic This is a molded container produced by blow molding a conductive resin tube. The many Layer containers are designed to prevent the ingress or egress of gases such as oxygen, carbon dioxide or water vapor. Non-reactive, acting as a barrier and preventing absorption of contained liquids by the vessel wall It has a relatively thin LCP layer that also acts as a conductive layer.   With respect to the term "layer", the present disclosure may, in some cases, refer to a number of individual intermediate-generated Describes laminated film structures, including films; in other cases, individual With different planar areas parallel to its main surface somewhat similar to the film Describes an integral film structure having different properties in different planar areas. "layer The use of a term such as "" refers to a planar area in an integral film; Should be understood as equivalent for each intermediate-produced film or portion thereof It is. The teachings throughout this disclosure will cover both these forms of LCP or TP film. It is understood that it applies equally to states.   The above and other objects, features and advantages of the present invention will be described with reference to the drawings. Will be better understood from the following detailed description of preferred embodiments of the invention. BRIEF DESCRIPTION OF THE FIGURES   FIG. 1 illustrates a twin-screw (2-annular) co-extrusion process according to a first embodiment of the present invention. FIG. 2 is a schematic view showing a partial cross-sectional view of a die.   2A-2C are schematics of an extruded film showing the form of an oriented polymer material layer therein. FIG.   FIG. 3 is a sectional view showing a detailed example of a die assembly of the type shown in FIG.   FIG. 4 is a cross-sectional view of the die assembly of FIG. 3, showing the support assembly.   FIG. 5 shows further details of the support assembly and also shows the drive assembly of FIG. -It is sectional drawing of an assembly.   FIG. 6 shows a second embodiment of the present invention, which is shown in FIGS. 1 and 3-5. 3 shows a triaxial (3-annular) die, which is a variant of.   FIG. 7 shows the molecular orientation of the film made by the die of FIG.   FIG. 8 shows a detailed example of a triaxial die assembly according to a third embodiment of the present invention. FIG.   FIG. 9 shows the shear pattern of the polymer flow through the device of FIG. Detailed description of the invention First specific example   FIGS. 1 and 3-5 disclose a first method and a first apparatus for carrying out the present invention. I do. FIG. 3 is a partial cross-sectional view of a die specifically adapted to perform the process of the present invention. FIG. Plasticization by melting or solvating liquid crystal polymer And then introduced into the inlet 51a. The LCP comprises a distribution channel 51a and It passes through the second distribution channels 51b and 51c. Channels 51a, 51b And 51c and 52a and 52b receive a plurality of each type of polymer. And put them in each channel 51a, 51b and 51c and 52a and Includes a plurality of individual distribution channels for passing to 52b.   The die assembly is generally indicated at 30, which includes three tubular rotors. , Inner tubular rotor 32, intermediate tubular rotor 34, and outer Including a tubular rotor 36. The cylindrical inner space or annular part 33 is a rotor It is defined between 32 and 34. Similarly, the outer annular portion 35 includes the rotors 34 and 36 Is defined between   After passing through the annular portions 33 and 35, the extruded LCP and thermoplastic resin Are two layers below the rotor 34 and between the lower parts of the rotors 32 and 36. At the exit space 37 defined by.   In this example, the lowermost edge of the rotor 34 has an annular thickness 37 Rotors 32 and 36 are substantially identical to those of sections 33 and 35. Downward-pointed shape corresponding to the shape of the opposing inner surface of the ape). However, this arrangement is not essential. For example, the cylindrical portion 34 Is at the same level as the lowest point of the cylinders 32 and 36, or Lower level. Other examples of advantageous structures can be found by experiment Some can be discussed below.   The flow of each LCP or thermoplastic resin is combined in space 37 resulting in a tubular Film 38 is formed and air is blown down and to blow the film. Extruded toward the outside of the channel 40 through which the fluid passes. For example, introduce blow air Piping joints can be placed at some point along the channel 40 for storage.   The inner and outer rotors 32, 36 are in a first orientation, for example, upper in this example. Can be rotated clockwise as viewed from the side. Intermediate rotor 34 is in the opposite direction That is, in this example, it can be rotated counterclockwise when viewed from above. The rotors 32, 34, 36 are connected to corresponding coaxial gears 32a, 34a, 36a. Have been. The gears are then driven by the corresponding pinions 32b, 34b, 36b Rotate. Advantageously, in this embodiment, the pinions 32b, 36b Can be mounted on a shaft. Because the rotors 32 and 36 are oriented in the same direction. Because they rotate in the same direction. Of course, a simple machine Due to mechanical deformation, each rotor rotates either clockwise or counterclockwise It can also be arranged as follows.   The circumferential shear pattern of the resulting film 38 is illustrated in the lower part of FIG. Understood As such, the opposing layers of polymer flow in the annular sections 33, 35 meet in space 37. These surfaces combine to form the center of the resulting film Then, it is sheared in the second orientation by the rotation of the intermediate rotor 34, thus The central portion of the lum is strongly oriented toward the second orientation. Conversely, inner and outer rows Rotation of the turrets is caused by the inner surface of the flow in the annulus 33 and the Causes the surface to be oriented in the first orientation. These two layers are obtained Forming the outer layer of the film.   The circumferential shear pattern illustrated in the lower part of FIG. Has a combined effect with the longitudinal shear pattern in the machining direction resulting from downward motion of the flow It should be understood that This long axis shear is applied to the annular portions 33 and 35 and the rotor. At each interface between the polymer streams in 32,34,36 will be the same.   FIG. 3 shows another embodiment of a die assembly 30 according to the present invention in detail in cross section. It is a detailed diagram. The inner rotor 32 rotates around the blast air channel 40. The LCP material is supplied to the inner annular portion 33 by the first pump 41. Thermoplastic The polymer material is supplied to the outer annular portion 35 by the second pump 42. pump 41 and pump 42 may be the same polymer or different polymers or May be supplied.   The inner annular portion 33 includes a seal 43 between the inner rotor 32 and the intermediate rotor 34. Define the lower side. Through the peripheral support structure illustrated at 50 through the flow path 51a A flow path is provided from the pump 41 to the annular portion 33. Further channels are with the support structure 50 A pair of seals 45, 47 between the outer rotor 36 and defined in the outer rotor 36. Flow path 51b, a pair of seals between the outer rotor 36 and the intermediate rotor 34 44, 46 and a flow path 51c in the intermediate rotor 34.   Similarly, the polymer is first pumped by the pump 42 into the channel 5 in the support structure 50. 2a, by a pair of seals 48, 49 between the support structure 50 and the outer rotor 36 The additional flow path defined, and then the flow path 52b formed in the outer rotor 36, Then, it is supplied to the annular portion 35.   Conventional discharge means, for example, with a seal 47 from any dead space 48 to the outside from the annular space between them.   FIG. 4 illustrates a die assembly 30 and a support assembly, generally indicated at 55. FIG. As can be seen in FIG. 4, the rotors 32, 34, 36 are cylindrically elongated. Concentric with the air channel 40 by the long portions 101, 102, 103 and extending upward I do. The extensions are further provided by corresponding flanges 104, 105, 106. It is growing. These flanges are the common axis of the rotor and channel 40 From the outside to the outside, in this embodiment, a conical orientation that extends upward at a constant angle It has the shape of a ring. As shown, in this example, the flange is generally Are parallel to each other.   The flange portion is further extended by the horizontal mounting portions 32c, 34c, 36c. You. These mounting portions are mounted on the mounting rings 56, 57, 58 by screws or the like. Is being worn. Each gear wheel 59, 60, 61 is provided with a mounting ring 56, 57, 5 8 at the top of the radial outwards. The function of the gear wheel will be further Discuss.   Without contacting the outside of the gearwheel, the enclosure for the support assembly is sealed. It is formed by a seamless metal cylinder 62 and the like. Ball bearing 63 Are mounted between the mounting rings 56, 57, 58 and the cylindrical portion 62. General A plate-shaped bottom cover 64 is fastened to the bottom of the cylindrical portion 62, I support it. The bottom cover 64 includes a generally cylindrical die surrounding the support structure 50. Outside the cover 65 (see FIGS. 3 and 4), supported by the top surface , Thereby surrounding the rotor and related structures.   The heat insulating ring 66 is supported on the die cover 65, and is supported from the die block. Prevent heat conduction to the drive train. As indicated by arrow 67, the cooling air Due to natural or forced convection, the flange portions 32b, 34b, the mounting ring 58 and Each hole, slot or the like in the bottom cover 64 can be freely passed. Fastened to the top of the cylindrical portion 62 is a top ring 68 on which is supported What is present is a top support cover 70. The top support cover 70 is attached to the hand knob 74. Thus, it is fastened to the top ring 68 by an operable screw 72 or the like. Top At least a part of the bush 76 mounted on the support cover 70 is empty. An air channel 40 is defined.   Referring again to FIG. 4, the mounting portions 32c, 34c of the rotors 32, 34, 36, 36c are radially staggered. That is, the mounting part 32c The mounting portion 34c extends radially further outward than the portion 34c, and the mounting portion 34c It extends radially outward farther than 36c. Correspondingly, mounting ring 5 8 extends radially inward farther from the support 63 than the mounting ring 57. The mounting ring 57 extends radially inward farther than the mounting ring 56. I do. With this structure, after the cover 70 is removed, The rotors can be easily removed individually if needed.   Further, all combinations of support assembly 55 and rotors 32, 34, 36 By simply removing the screws holding the cover 65 to the bottom cover 64, the unit It can be easily removed from the die cover 65 as a socket. Thus, die assemble Repairs such as re-combination with channels 51a, 52a and die cover 65 Block the polymer supply structure and appropriate plumbing fittings including the corresponding channel Easy to do without having to. Also, do not obstruct the removal of the rotor. I FIG. 4 shows an electric heater 78 also shown in FIG. It is also provided in the die cover 65 for heating. The heater 78 is a bush It is fastened in the heat insulating ring 66 by a tool 80 or the like. Electric wire 81 is a heater 78 to provide power.   Advantageous features of the structure of FIG. 4 include a heater 78, a polymer feed facility and a rotor. Are located below the bottom cover 64 and the isolation ring 66, and the die cover 65 Located below the top surface of the device. Thus, sir Total heat release in the case of tropic polymers or lyotropic polymer Solvent is located at the bottom of the device, which allows the support assembly and drive Any adverse effects on the assembly are prevented.   FIG. 5 shows further details of the support assembly 55 and the drive assembly 82. . Slots, etc. are formed in the cylindrical part 62 adjacent to the gear wheels 59, 60, 61 Have been. Each pinion 84, 85, 86 rotates a gear wheel and To the outside of the gear wheels 59, 60, 61 so that the rotor rotates. , And are fitted to it. Motors, reduction gears, etc. Assembly 87 is mounted on top ring 68 and partially supported by ON 84 is driven. Preferably, two additional motors, reduction gears, etc. It is arranged to drive the pinions 85 and 86 independently. Three separate motors Is optimized over the rotor speed to fine tune the shear forces on the polymer. It is expected to give good control. Second specific example   According to another aspect of the invention, an advantageous type of shear similar to that shown in FIG. The break pattern can be obtained by another method. Two reversing mandrels A conventional extrusion die having a structure as shown in FIG. Produces balanced biaxial films of thermoplastic polymers or their blends It is known to We have found that conventional film layer formation and film Two such layers can be joined together using a bonding apparatus and method, thereby providing a It has been found that a bonded film having a shear pattern of Third specific example   6 and 7 illustrate another method and apparatus embodying the present invention. You. FIG. 6 shows a three-axis (three-annular) die, which is illustrated in FIGS. 1 and 3-5. This is a modification of the example. This device differs from that in the first embodiment in order to eliminate redundant explanations. Only the parts of the example will be discussed.   In this embodiment, the inner rotor 32 and the outer rotor 36 are opposite Driven by corresponding gears 32a, 32b, 36a, 36b. The non-rotating member 34 'is an inner rotor at a position corresponding to that of the intermediate rotor 34 in FIG. Between the rotor and the outer rotor. The coaxial annular channel is a non-rotating member 3 4 '. The orientation of the film produced by this die Also shown at the bottom of FIG. 6 and also in FIG. Can make up about 90% of the film thickness The substantially central core layer of the resulting film is oriented in the machine direction. Polymer material Is supplied to the inner annular portion 33 and the outer annular portion 35, which may be the same or different. The reverse inner rotor 32 and the outer rotor 36 Thus, ratios that may act on each, each of which may constitute approximately 5% of the thickness of the film Produces a relatively thin surface layer. The thickness of the surface layer controls the polymer flow rate Therefore, it can be adjusted as desired. These surface layers are complementary to the machining direction Oriented. On the surface of the film, the orientation is advantageously +/- 45 °. You. The orientation angle gradually decreases between the surface and the central core layer, thereby causing the orientation of the orientation to decrease. The direction gradually becomes the machining direction.   The flow in the three concentric annular channels is composed of the same polymer or polymer blend. It should be understood that this need not be the case. For example, the LCP is Flowable through the blended polymer (LCP + TP) or thermoplastic resin. The rimmers can flow in the outer and inner annuli 33 and 35. Typically, this No co-extrusion was performed in the type of device. Specific examples of coextrusion are given below Discuss.   The extrudate formed according to FIGS. 6 and 7 is slit into a film or sheet. It can be shaped or remain tubular. Substantive A substantially uniaxial central core layer is applied to the resulting film or tube using conventional methods. Greater tensile and compressive strength in the machine direction than products made with The degree (Young's modulus) is given. The strength of the tube or film is non-rotating annular It rises depending on the amount of material passing through 39. For example, lower strength but more flexibility If necessary, supply less material through the non-rotating annulus 39 Can be. This embodiment provides several advantages of a balanced biaxial film. A very strong tube that also has enhanced strength with a uniaxial central core layer or A film is made. Fourth specific example   According to another aspect of the present invention, shown in FIGS. 8 and 9, in the intermediate rotor 34 '' By arranging the formed central annular portion 39 ', the embodiment shown in FIGS. The example was modified. The material passes from the pump 3 indicated by 53 through the flow paths 54a, 54b. The flow path is sealed by a further seal 92.   In the apparatus of FIG. 8, preferably, the intermediate rotor 34 '' rotates slowly. To minimize the helical orientation of the central core layer resulting from rotation of the intermediate rotor 34 ''. You. The outer and inner rotors 32, 36 are preferably at the same rotational speed and Rotating together in paired orientations produces the shear pattern shown in FIG. Outside And the inner rotor preferably rotates at a higher rotational speed than the intermediate rotor. You.   In FIG. 9, the central core layer 93 has been slightly sheared by the movement of the intermediate rotor. Thus, at a small angle defined as a negative angle to the machining direction Oriented. Each outer layer 95a, 95b is preferably less in the machine direction. Both are oriented at a plus angle of 5 °. The angle of orientation of the surface layer should be as large as possible Should. Gradual between the positive angles of the surface layers 95a, 95b and the core layer 93 The transition occurs in the middle layers 94a, 94b.   Co-extrusion of different liquid crystal, thermoplastic and blend polymers In the same manner as in the previous specific example, this specific example is also possible. Of thermoplastic polymer One of them is an adhesive or "tie layer" between the LCP layer and another TP layer. ) ". In the past, coextrusion was typically performed with the apparatus shown in FIG. Not. Co-extrusion of LCP and TP   As mentioned above, in connection with the first to fourth embodiments, the thermoplastic polymer and And LCP in combination with blended polymers, as described in connection with FIGS. 1-9 The method and apparatus can be used to make multilayer coextrudates.   Coextrusion of polymers is known per se. Thermotropic liquid crystal polymer (LCP) and thermoplastic resin are fed through a co-extrusion die Tomanifold coextrusion (see, for example, Osborn, K. et al. R. And Jenkins, W.S. A. , Pla stic Films, Technical, 1992, pp. 118-129). And simultaneous extrusion (simultaneous extrusion). Many types of polymers are homogeneous Using a die where two or more melt streams converge on different layers for a thin stream and accumulate in them Co-extruded. Such a die has a flat surface for producing a flat film or sheet. Can be or circle to make tubular film or cylinder It can be shaped.   When using LCP in conventional coextrusion dies, long and rigid LCP molecules are primary It tends to align in the flow direction (machining direction), which creates a uniaxially oriented LCP layer. To achieve. The LCP layer is very weak transversely to the machine direction, This is undesirable as it easily tears along the length of the tube or tube . This anisotropy is a common property of conventionally extruded LCPs, Overcome by imparting a biaxial orientation in the extrusion die before extrusion from the die (For example, US Pat. No. 4,939,235; incorporated herein by reference) 4,966,807; and 4,975,312).   Therefore, the LCP layer or layers may comprise a thermoplastic polymer or LCP-thermoplastic Biaxial orientation in layers or multi-layers with resin blends and existing improved coextrusion L It is desirable to make CPs and thermoplastic films, sheets or tubes. Fifth specific example   The product of this embodiment has an LCP on one side and a thermoplastic resin on the other. A multi-layer film, sheet or tube having It is axially oriented and is 5% to 95% of the total thickness. The coextruded film is almost 0. 0002 to 0. 010 inches (0. 005-0. 25mm) thick and the sheet is 0. 010 to 0. 100 inches (0. 25-2. 5mm) thick and the tube is 0.3mm 00 05 to 0. 100 inches (0. 01-2. 5 mm).   The device in FIG. 1 has two types of polymers, one is Vectra^R, Xydar^ROr anisotropic A thermotropic LCP, such as another polymer capable of forming a melt; , Polyethylene terephthalate, polybutylene terephthalate, polynaphthalene Terephthalate, polyamide, polyimide, polyarylene ether ketone, Phenylene sulfide, polycarbonate, polystyrene or polyolefin Used with thermoplastic polymers such as The LCP is, for example, the first LCP shown in FIG. Pumped by a pump 41, the thermoplastic resin is pumped by a second pump 42 Pumped. Alternatively, the LCP is pumped by a second pump and It is understood that the plastic can also be pumped by the first pump. . If the two streams meet at area 37, each polymer will wrap around the tube extrudate. They form different layers so that they are continuous. The relative thickness of each layer is Controlled by flow and the size of the annular channel area indicated by 33 and 35 I do. The LCP flow from Pump 1 is half that of the thermoplastic from Pump 2. In this case, the thickness of the LCP will be approximately one-half that of the thermoplastic. Ring The pressure in the LCP in the section 33 is maintained approximately equal to the pressure of the thermoplastic resin in the annular section 35. If the flow from pump 1 is half of that from pump 2, The width of the annular portion 33 must be approximately half that of the annular portion 35. LCP layer Is about 5% to 95% of the total film thickness, and the total film thickness is about 0.0002 inches. H In this way, layers of various thicknesses are prepared so that the thickness can be reduced to 0.010 inches. can do. Coextruded sheets can be made using a similar method. But 0.010 to 0.100 inch thicker with larger die gaps Can be made. Tubes, pipes and cylinders are also about 0.0005 It can be co-extruded in this way with a wall thickness of You.   In order to cause biaxial orientation in the LCP layer, LCP must be present in the annular portion 33. The die components 32 and 34 rotate in opposite directions to each other . If the LCP is present in the annulus 35, the die components 36 and 34 Rotate in opposite directions. These die components, which are the boundaries of the LCP flow Reversal of the components is required in the LCP melt by the shear forces that orient the LCP molecules. Generate the required lateral orientation. The biaxially oriented LCP flow is in the region 37 with the thermoplastic flow When combined, the relatively long relaxation time of the LCP results in biaxial orientation of the LCP layer. Is held.   The thermoplastic resin layer can be biaxially oriented by the rotating action of the die, The degree of orientation retained by the plastic resin will depend on its relaxation time .   The coextrusion of the present invention can be performed with polymers having similar or different melting points. LC P and thermoplastic layers are co-extruded and have a melting point of about the same or about 3 If within 0 ° C., all die components will be at approximately the same temperature. If they are not within approximately 50 ° C. of each other, die component 3 2 and 36 should include separate heaters to control the temperature of the Pumps 41, 42 and polymer delivery tubes 51a, 52a Will be maintained at different temperatures corresponding to the points. The two flows meet in area 37 If they reach a similar temperature in a short time, then cool after leaving the die. I do. During this cooling process after exiting the die, the coextruded film is Can be biaxially stretched by the internal pressure and longitudinal stretching of the extrudate.   For example, Vectra^R type A-950 (Hoechst-Celanese Corporation) Thermotropic LCP converts both polymers to a temperature of about 280-300 ° C. While coextruding with PET type 13339 (Eastman Chemical) Can be. The die component rotates in the opposite direction as described above. About 10 to 1000 seconds^-1Of shear in the LCP melt stream. Chu The extrudate has two orthogonal draw ratios between 1.5: 1 and 40: 1, two orthogonals after discharge. Stretch in the direction. Sixth specific example   The product of this sixth embodiment comprises three layers: 10% to 90% of the total thickness Biaxially oriented LCP layer on one side, first heat transfer layer on LCP layer containing at least 5% of total thickness A plastic resin layer and an LCP layer comprising at least 5% of the total thickness or the first thermoplastic A second thermoplastic resin layer over any of the resin layers.   The apparatus of FIG. 8 may be used in the following manner, for example, using two or three polymers, Can be pumped from pumps 1, 2 and 3:     a) Pump 1: thermoplastic resin A           Pump 2: LCP           Pump 3: Thermoplastic resin B     b) Pump 1: LCP           Pump 2: thermoplastic resin A           Pump 3: Thermoplastic resin B   The LCP can be the same material as in the first coextrusion embodiment. Thermoplastic resin A or B, polyethylene terephthalate, polybutylene terephate Talate, polynaphthalene terephthalate or other polyester, polyamide , Polyimide, polyarylene ether ketone, polyphenylene sulfide, polycarbonate -Polymer such as carbonate, polystyrene or polyolefin It is understood that you can do it. In addition, the thermoplastic resin A or B is LCP and one or more. of It is also understood that the blend can be a thermoplastic polymer. Furthermore, pumps 1, 2 Or 3 in any order with thermoplastic resin A or B or LCP It is understood that you can do it.   To create a biaxial orientation in the LCP layer, the die component 32 in FIG. , 34 '' and 36, as described in the first coextrusion embodiment. Cause lateral shear in the LCP melt stream. In the case of the above example (b) Rotates, for example, the inner rotor 32 and the central rotor 34 '' in opposite directions. Causing lateral shear in the LCP layer. Transverse shear is the opposite Due to the interface moving in the orientation, L in the annulus 33 supplied by the pump 1 Applies to CP melt. Alternatively, the LCP can be supplied by pump 2 and The components 34 '' and 36 can be rotated in opposite directions. It is understood that.   In a preferred embodiment of the embodiment (a), the thermoplastic resin A is 13339 (Eastman  Chemical Co., Ltd.), LCP is Vectra^RA-950 (Hoechst-Celanese Made by the company). The flows from the pumps 1, 2 and 3 are almost equal and the thermoplastic resin A And each layer of the LCP layer is substantially equal. The total film thickness is about 0.0005 to 0.0 10 inches.   Alternatively, the LCP flow from Pump 3 is about the same as the flow in Pumps 1 and 2. It can be slowed down from 1/2 to 1/10, which reduces the LCP layer thickness to thermoplastic resin It is about 1/2 to 1/10 that of the layer. For thinner LCP layers, the ring 39 'is small in proportion to the annular portions 33 and 35, Approximately equal pressures must be maintained when combined. Die temperature is almost At 270-300 ° C., the inner rotor 32 and the center rotor 34 ″ Rotate in the direction to apply LCP flow in the annular portion 35 for about 10 to 1000 seconds.^-1Shearing A velocity is created to create a biaxial orientation. When the LCP is delivered by Pump 1 , The inner rotor 32 and the central rotor 34 '' rotate. LCP for pump 2 Thus, when delivered, the outer rotor 36 and the central rotor 34 '' rotate. The tube extrudates are extruded at a biaxial draw ratio of between 1.5: 1 and 40: 1 after extrusion. Horn Companded in orthogonal directions.   The orientation in the LCP layer is determined by the pump flow, die size, die rotation speed, What is controlled by the low-up ratio and the longitudinal stretching ratio to the extrudate is Understood.   The non-rotating annular portion 39 in the die component 34 'shown in FIG. The gear 34a and the pinion so that the component 39 rotates at a controllable speed. It is also understood that at 34b, it can be rotated by the same type of operating mechanism as shown in FIG. You. Seventh specific example   The product of this embodiment comprises 10% to 90% of the film thickness, Has a biaxially oriented LCP layer, and has a thermoplastic resin layer on either side of the LCP layer. A multilayer film, where each thermoplastic layer is at least 5% of the total film thickness And the thermoplastic resin layers are made of the same or different thermoplastic resin materials. LCP And the thermoplastic polymer can be the same as in the first coextrusion embodiment. You.   Use the apparatus of FIG. 6 where the central rotor 34 is stationary. Central rotor recessed Outlet of the die formed by the outer rotor 36 and the inner rotor 32 Thus, an outflow space shown in FIG. 6 is formed. The central component 34 'is shown in FIG. LC by a polymer pump corresponding to pump 53 (herein referred to as pump 3) An annular portion 39 for feeding P is included. The annular portions 33 and 35 correspond to those in FIG. Pumps 1 and 2.   The thermoplastic resin A is supplied by the pump 1 and the thermoplastic resin B is supplied by the pump 2. Is sent. The thermoplastic resins A and B may be the same, the first and the second It may be a thermoplastic polymer such as those described in the specific coextrusion example 2 above. L CP is pumped by the pump 3 and into the annulus 39 in the central component 34 '. Will be delivered. The LCP flows out of the central component 34 'and the inner rotor 32 and Flows out of the die gap (outflow space 37) formed by the outer rotor 36 and the outer rotor 36. You Before contact with the thermoplastic resin in the annular portions 33 and 35. This connection Touch time should be controlled by the flow speed from the pump and the length of the rotor And preferably 0.1 to 10 seconds.   The inner and outer rotors rotate in opposite directions to each other and the central component 34 'is stationary. Contact between the end of the central component and the outlet of the die In region 37, through different rotations of the thermoplastic in the annular portions 33 and 35 Lateral shear is applied to the LCP layer. This lateral shear gives the LCP layer biaxial orientation. Generate. The degree of lateral orientation is: rotor speed, polymer flow from the pump The viscosity of the thermoplastic resin (s), and the central rotor is recessed from the die outlet Distance. Preferably, the rotation speed is thermoplastic and LC 10 to 1000 seconds for P layer^-1That would result in a shear rate of   In a preferred embodiment, the LCP is Vectra^RA-950 (Hoechst-Celanese) The thermoplastic resins A and B are the same polymer, namely PET13339 (Eastman Chemi cal company). The die temperature is between 270 and 300 ° C. The tube extrudate It is biaxially stretched after extrusion so that the biaxial draw ratio is between 1.5: 1 and 40: 1. You. Eighth specific example   The product of this embodiment may comprise one or more thermoplastic polymer layers or one or more LCP- Multilayer with biaxially or multiaxially oriented LCP layer combined with thermoplastic polymer blend layer It is a layer container. Using the apparatus of FIG. 1 or FIG. Can be co-extruded. Thermoplastic polymer Blow molding processes for are well known (eg, Schwartz, SS and Sidney H. Goodman, Plastics Materials and Processes, Van Nostrand Reinhold  Company, 1982, pp. 617-631).   Preferably, the central rotor 34 '' and the inner rotor 32 rotate in opposite directions. And the outer rotor 36 is stationary or in the same orientation as the inner rotor 32 Use the device of FIG. 8 which is either rotating. The annular portion 33 shown in FIG. As a pump 1, LCP is fed by a polymer pump or an extruder shown in FIG. As shown in FIG. 8, the annular portion 35 feeds the thermoplastic resin A from the pump 2, The annular portion 39 ′ feeds the thermoplastic resin B from the pump 3.   It is understood that thermoplastic resins A and B may be the same. As an alternative The thermoplastic resin B is an adhesive or a binder that preferentially bonds the LCP layer to the thermoplastic resin A. May be a tie layer. The three annular streams 33, 39 'and 35 are made of plastic. With a multi-layer tube 38 called a parison hanging from the die And spills out of the die. The tubular parison is sandwiched between the two mold halves. Rare, then rotating pipe joints joined at a point along the channel 40 shown in FIG. Pressurized by compressed gas supplied through Multi-layer LCP-thermoplastic Paris When the son has fully extended against the mold wall, it is cooled and the method referred to above Is removed from the mold. The result is a multi-layer with a thin multi-axis oriented LCP layer inside. It is a layer bottle.   The degree of lateral orientation in the LCP layer depends on the rotational speed of rotors 32 and 34 '', It will depend on the flow rate of the LCP from the pump and the size of the die. Preferably Means that the rotation speed is 10 to 1000 seconds in the thermoplastic resin and the LCP layer^-1 Will produce a shear rate of   In a preferred embodiment, the LCP (inner layer) is Vectra^RA-950 (Hoechst-Celanese The thermoplastic resin A (outer layer) is PET13339 (Eastman Chemical). The thermoplastic resin B (intermediate layer) is Vectra^R50:50 blur between A-950 and PET13339 And The die temperature is between 270 and 300 ° C. Molded size is 1 liter The diameter of the tubular parison is 10 to 20 mm. Final multi-layer bottle The wall is approximately 0.25 with an LCP layer approximately 0.01 to 0.10 mm thick. It is 0.50 mm thick.   This embodiment meets the required standards for some industrial containers. Inside L The CP layer packages food products such as tomato, peach and orange juice. It provides a good oxygen barrier necessary for It is also used for corrosive industrial chemicals. Sometimes inert to the material. Generally, the containers have thinner walls than conventional containers. While delivering light weight, it delivers high performance at low cost.   It also meets the stringent requirements for beer bottles and other beverage containers. You. For example, PET extruded beer bottles have not been satisfactory. example If so, there are numerous fragrance changes. Than standard single layer PET bottles have It is also necessary to improve the oxygen permeability 5-10 times lower, which is provided by this example. Is done.   Oxygen permeability of approximately 0.1 theoretically at a thickness of about 1.25 mm (0.05 inch) Is 0.1 oxygen equivalent to a conventional PET bottle that can theoretically obtain Transmission can be obtained with an LCP layer that is only 0.01 mm (0.0004 inch) thick. Can be. A 0.1 mm thick LCP layer can provide an oxygen permeability of 0.004. found.   0.05-0.10 per 100 square inches over 24 hours at 1 atmosphere partial pressure Oxygen permeability as low as 0.015 cc and 0.001 inch (0.025 mm) Provided by a thick LCP layer. The inner LCP layer also absorbs the flavor of the beer or More than 10 times lower in liquid or gas solubility, unchanged. Also it is It is also better than PET as a carbon dioxide barrier.   In another example, Vectra^RXydar instead of^R0.006 mm L using The CP layer provides an oxygen permeability of 0.7, which can be used in beverage containers, but Vectra in the example above^RNot as good as can be obtained with   Although the invention has been described herein with reference to particular embodiments and embodiments thereof, The appended claims are not limited to this disclosure. For example, LCP and heatable Any combination of plastic polymers or blends thereof may be used with any of the devices herein. Can be used with the device. The present invention falls largely within the teachings herein. It is intended to embody all modifications and variations that may occur to those skilled in the art.

──────────────────────────────────────────────────の Continuation of front page (51) Int.Cl. ⁶ Identification symbol FI // C09K 19/38 B65D 1/00 BC (81) Designated country EP (AT, BE, CH, DE, DK, ES, FI , FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), UA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, CA, CN, EE, GE, JP, KR, LT, LV, MX, SI, TR, UA, UZ, VN

Claims (1)

Claims 1. A multilayer container prepared from one or more liquid crystal polymers (LCP) and one or more thermoplastic polymers (TP), wherein at least one LCP layer has a controlled molecular orientation. 2. The multilayer container of claim 1, wherein the layers of LCP and TP are arranged in an intermediate layer and an outer layer covering at least one inner layer, wherein the LCP layer is an inner layer and at least one TP layer is an outer layer. . 3. The multilayer container according to claim 2, wherein the LCP is Vectra ^R A-950 and the outer layer is PET13339. 4. 3. The multilayer container of claim 2 wherein said container is approximately 0.25-0.50 mm thick and said LCP layer is approximately 0.01-0.10 mm thick. 5. The multilayer container according to claim 2, wherein the intermediate layer is an adhesive layer. 6. The multilayer container according to claim 5, wherein the LCP is Vectra ^R A-950 and the outer layer is PET13339. 7. multilayer container according to claim 6, wherein said intermediate layer is a blend of Vectra ^R A-950 and PET13339. 8. 3. The multi-layer container of claim 2, wherein said container is a bottle having an oxygen permeability of less than about 0.004-0.7 cc per 100 square inches per 24 hours at 1 atmosphere. 9. 9. The multi-layer container of claim 8, wherein said oxygen permeability is less than about 0.05-0.10 cc per 100 square inches per 24 hours at 1 atmosphere. 10. Using a tubular die having at least three coaxial mandrels including an outer, inner and intermediate mandrel forming two annular flow channels therebetween, and a third annular flow channel within the intermediate mandrel; Rotating at least two of the mandrels; combining each of the polymer films formed in the channel to form a tubular parison; and then blow molding the tubular parison. A method for producing a multilayer multiaxially oriented container from a liquid crystal polymer and a thermoplastic polymer, comprising a step of forming a container. 11. The method of claim 10, wherein the outer and inner mandrels rotate in the same orientation. 12. The method of claim 11, comprising forming the multilayer film such that the molecular orientation of one side of the intermediate plane of the film is substantially a mirror image of the orientation of the other side of the intermediate plane. 13. The method of claim 10, wherein the intermediate mandrel rotates in an opposite orientation from the inner mandrel. 14． 14. The method of claim 13, wherein the outer mandrel does not rotate. 15. The method of claim 10, wherein the LCP and TP layers are aligned with an intermediate layer and an outer layer covering at least one inner layer, wherein the LCP layer is an inner layer and at least one TP layer is an outer layer. 16. The LCP is a Vectra ^R A-950, The method of claim 1 5, wherein said outer layer is PET13339. 17． 16. The method of claim 15 wherein said container is approximately 0.25-0.50 mm thick and said LCP layer is approximately 0.01-1.10 mm thick. 18. The method according to claim 15, wherein the intermediate layer is an adhesive layer. 19. The LCP is a Vectra ^R A-950, The method of claim 1 8 wherein the outer layer is PET13339. 20. The method of claim 19, wherein said intermediate layer is a blend of Vectra ^R A-950 and PET13339. 21. 16. The method of claim 15, wherein said tubular parison is blow molded to form a bottle having an oxygen transmission rate of no more than about 0.004-0.7 cc per 100 parallel inches per 24 hours at 1 atmosphere. 22. 22. The method of claim 21 wherein said oxygen transmission rate is less than about 0.05-0.10 cc per 100 parallel inches per 24 hours at 1 atmosphere.